JPS61178411A - Production of granular active carbon - Google Patents
Production of granular active carbonInfo
- Publication number
- JPS61178411A JPS61178411A JP60020667A JP2066785A JPS61178411A JP S61178411 A JPS61178411 A JP S61178411A JP 60020667 A JP60020667 A JP 60020667A JP 2066785 A JP2066785 A JP 2066785A JP S61178411 A JPS61178411 A JP S61178411A
- Authority
- JP
- Japan
- Prior art keywords
- binder
- coal
- activated carbon
- desulfurization
- active carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、石炭を主原料とする脱硫用活性炭の製造法
に間するもので、特に吸着能および機械的強度の優れた
脱硫用活性炭の製造方法に間する。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for producing activated carbon for desulfurization using coal as a main raw material, and in particular, a method for producing activated carbon for desulfurization that has excellent adsorption ability and mechanical strength. in between.
従来の技術
排煙脱硫法として種々の方法が提案されているが、石炭
火力発電所等の場合、その立地条件などから排水および
用水量の少なくてすむ乾式法が脚光を浴びてきている。BACKGROUND OF THE INVENTION Various methods have been proposed as flue gas desulfurization methods, but in the case of coal-fired power plants, etc., the dry method, which requires less wastewater and water consumption, has been attracting attention due to its location and other factors.
しかも副産物とし、石膏を回収する方法にかわり、元素
イオウを回収する方法が乾式法の主流となってきている
。Moreover, instead of the method of recovering gypsum as a by-product, a method of recovering elemental sulfur has become the mainstream of the dry method.
乾式法は、石炭燃焼排ガス中の502を脱硫剤である活
性炭に吸着させ、SO2を吸着した活性炭は加熱脱着に
より再生し、循環使用する方法が主流である。このため
、活性炭は必然的に吸着塔・加熱脱着再生塔を循環移動
することになり、循環過程で損耗する。活性炭のサイズ
としては、吸着塔での通風圧力損失等を考慮して、5〜
10mmのものが主に用いられているが、循環過程で微
粉化した活性炭は、吸着塔で通風圧力損失を増加させる
。このため、循環過程で分級し除去することが必要であ
る。また、加熱脱着時には、吸着したSO2の離脱に際
し、活性炭のカーボンの一部が消費される。The mainstream dry method is a method in which 502 in coal combustion exhaust gas is adsorbed on activated carbon, which is a desulfurization agent, and the activated carbon that has adsorbed SO2 is regenerated by thermal desorption and recycled. Therefore, the activated carbon inevitably circulates through the adsorption tower and the thermal desorption/regeneration tower, and is worn out during the circulation process. The size of the activated carbon is 5 to 5, taking into consideration ventilation pressure loss in the adsorption tower, etc.
Although 10 mm diameter activated carbon is mainly used, the activated carbon that is pulverized during the circulation process increases ventilation pressure loss in the adsorption tower. Therefore, it is necessary to classify and remove them in the circulation process. Furthermore, during thermal desorption, part of the carbon in the activated carbon is consumed when the adsorbed SO2 is released.
すなわち、脱硫用活性炭は消耗品であり、脱硫プロセス
においては、損耗量と同量の活性炭を循環系に補給する
必要がある。このため、損耗量が多いとランニングコス
トが高くなり、ひいては脱硫コストを左右することとな
る。また、火力発電所の規模が大きくなるLこ従い、活
性炭も多量に必要となる。このため、脱硫用活性炭とし
ては、安価で、サイズのそろった、しかも吸着能と共に
耐衝撃強度、耐磨耗強度等の機械的強度の優れた活性炭
が求められている。That is, activated carbon for desulfurization is a consumable item, and in the desulfurization process, it is necessary to replenish the circulation system with activated carbon in an amount equal to the amount consumed. For this reason, when the amount of wear is large, running costs increase, which in turn affects desulfurization costs. Furthermore, as the scale of thermal power plants increases, a large amount of activated carbon is also required. For this reason, there is a demand for activated carbon for desulfurization that is inexpensive, uniform in size, and has excellent adsorption capacity as well as mechanical strength such as impact strength and abrasion resistance.
このような活性炭を得るには、安価で且つ供給の安定し
ている石炭を主原料とした粒状活性炭を製造するのが得
策であるが、石炭を主原料とする粒状活性炭では、吸着
能をたかくすれば機械的強度が低下し、反対に機械的強
度を強くしようとすれば、吸着能が低下するのが一般的
傾向である。In order to obtain such activated carbon, it is a good idea to manufacture granular activated carbon using coal as the main raw material, which is inexpensive and has a stable supply. If so, the mechanical strength will decrease, and conversely, if the mechanical strength is increased, the adsorption capacity will generally decrease.
例えば、非粘結炭、粘結炭およびバインダーの混合物を
成形し、得られた成形炭をロータリーキルン内で炭化処
理して脱硫用炭素材を製造する方法において、酸素3〜
lO容量%および水蒸気20〜80容量%を含有する加
熱ガスを、ロータリーキルンへ供給される成形炭1kg
当り1〜1ONTr?/hrの割合でロータリーキルン
へ供給し、且つ、ロータリーキルンの成形炭導入端部の
気相温度を450〜650℃、導出端部の気相温度を8
00〜1000℃に保持することを特徴とする脱硫用炭
素材製造法(特開昭57−129813号公報)、ある
いは、褐炭又は亜瀝青炭を500μ以下に粉砕し、水分
が10〜20wt%になるように乾燥したのち、該褐炭
、亜瀝青炭又はその混合物に対し0.3〜2.5wt%
の無機粘結剤を添加して5〜15+wmφに造粒成形し
、しかる後に不活性ガス又は燃焼ガス中において、温度
700〜b
昇温遼度1〜5℃/分で乾留することを特徴とする吸着
剤の製造方法(特開昭56−100123号公報)等積
々の提案も行われているが、必ずしも満足すべきもので
はない。For example, in a method for manufacturing a carbon material for desulfurization by molding a mixture of non-caking coal, caking coal, and a binder, and carbonizing the resulting molded coal in a rotary kiln, oxygen
1 kg of briquette coal is fed to a rotary kiln with heating gas containing 10% by volume and 20-80% by volume of water vapor.
1~1ONTr per hit? /hr to the rotary kiln, and the gas phase temperature at the inlet end of the rotary kiln is 450 to 650°C, and the gas phase temperature at the outlet end is 850 to 650°C.
A method for producing a carbon material for desulfurization characterized by maintaining the temperature at 00 to 1000°C (Japanese Unexamined Patent Publication No. 57-129813), or grinding lignite or subbituminous coal to 500μ or less and having a moisture content of 10 to 20 wt%. After drying as described above, 0.3 to 2.5 wt% of the lignite, subbituminous coal or mixture thereof.
It is characterized by adding an inorganic binder of 5 to 15+wmφ and granulating it to a size of 5 to 15+wmφ, and then carbonizing it in an inert gas or combustion gas at a temperature of 700 to 700°C and a temperature increase of 1 to 5°C/min. A number of proposals have been made, such as a method for producing an adsorbent (Japanese Patent Laid-Open No. 100123/1983), but these are not necessarily satisfactory.
解決しようとする問題点
この発明は、石炭を主原料として機械的強度が大きく、
かつ、吸着能の優れた脱硫用粒状活性炭を製造する方法
を提供するものである。Problems to be Solved This invention uses coal as the main raw material and has high mechanical strength.
Furthermore, the present invention provides a method for producing granular activated carbon for desulfurization that has excellent adsorption ability.
問題点を解決するための手段
この発明は、非粘結炭にバインダーを配合し、場合によ
っては必要な添加剤を添加して混練し、得られた混練物
を成形したのち炭化・賦活して脱硫用粒状活性炭を製造
する方法において、バインダーの一部として石油系重質
油を熱処理して得た軟化点150℃以上、H/Co、6
〜1.0の特殊粘結剤を添加することを特徴とする粒状
活性炭の製造方法である。Means for Solving the Problems This invention involves blending a binder with non-caking coal, adding necessary additives as the case may be, kneading it, molding the resulting kneaded product, and then carbonizing and activating it. In a method for producing granular activated carbon for desulfurization, a softening point of 150° C. or higher obtained by heat treating petroleum heavy oil as part of the binder, H/Co, 6
This is a method for producing granular activated carbon characterized by adding a special binder of 1.0 to 1.0.
作 用
この発明において用いる非粘結炭としては、粘結性のな
い亜炭、褐炭、亜瀝青炭、無煙炭の1種または2種以上
が挙られる。特に平均反射率(Rも)0.3〜0.8の
褐炭または亜瀝青を用いると好ましい結果が得られる。Function The non-caking coal used in this invention includes one or more of non-caking lignite, lignite, subbituminous coal, and anthracite. In particular, preferable results are obtained when lignite or subbituminous coal having an average reflectance (R) of 0.3 to 0.8 is used.
また、バインダーの一部として使用する特殊粘結剤とし
ては、石油系減圧蒸留残査油等の重質油を熱分解して得
られる軟化点150℃以上、H/Cが0.6〜1.0好
ましくは0.7〜0.9のピッチ状物質を使用する。In addition, the special binder used as part of the binder is obtained by thermally decomposing heavy oil such as petroleum-based vacuum distillation residue oil, and has a softening point of 150°C or higher and an H/C of 0.6 to 1. 0.0, preferably 0.7 to 0.9 pitch material is used.
この特殊粘結剤は、通常のコールタールピッチに比して
水素含有量が高いが、分子量が大きいため、乾留時の炭
化歩留りが高いにもかかわらず石炭質との反応性が良好
であり、石炭質と相互に溶融して強固な炭化物を形成す
る。This special binder has a higher hydrogen content than normal coal tar pitch, but because of its large molecular weight, it has good reactivity with coal, even though it has a high carbonization yield during carbonization. It melts with coal and forms a strong carbide.
これらの非粘結炭、特殊粘結剤は、配合した後、あるい
は配合する前に微粉砕するが、粉砕の程度は全量100
s+esh以下とするのが好ましい。These non-caking coals and special caking agents are finely pulverized after or before blending, but the degree of pulverization is 100% in total.
It is preferable to set it to s+esh or less.
微粉砕の後、バインダーとして特殊粘結剤とコールター
ル、バルブ廃液等の通常使用される成形用バインダーを
用い、これと非粘結炭を配合し、さらに必要ならば、成
形を容易にする添加剤を加え、ニーダ−1高速混練機等
で十分混練する。非粘結炭とバインダーとの配合物中の
非粘結炭の適切な配合割合は、非粘結炭の銘柄によって
異なるが、通常60%以上、好ましくは70〜90%配
合する。After pulverization, a special binder and a commonly used molding binder such as coal tar or valve waste liquid are used as binders, and non-caking coal is blended with this, and if necessary, additions are made to facilitate molding. The mixture is thoroughly kneaded using a high-speed kneader such as Kneader 1. The appropriate blending ratio of non-caking coal in the blend of non-caking coal and binder varies depending on the brand of non-caking coal, but is usually 60% or more, preferably 70 to 90%.
また、特殊粘結剤の配合割合は、4%以上配合するのが
好ましい。成形を容易にする添加剤としては、最も単純
な物質例としては水がある。Further, the blending ratio of the special binder is preferably 4% or more. The simplest example of an additive that facilitates molding is water.
混練物の成形は、ブリケットマシン、押し出し成形機等
を用いて行われ、直径3〜15fflls好ましくは5
〜10m−のアーモンド型、枕型、円柱状等の形状に成
形する。成形物の強度は、後述する磨耗強度および圧潰
強度がそれぞれ70%以上、0.2kg/P以上、好ま
しくは、80%以上、1.0kg/P以上となるように
成形する。The kneaded product is formed using a briquette machine, an extrusion molding machine, etc., and is preferably 3 to 15 fflls in diameter.
Shape into an almond shape, pillow shape, cylinder shape, etc. of ~10 m. The strength of the molded product is such that the abrasion strength and crushing strength, which will be described later, are respectively 70% or more and 0.2 kg/P or more, preferably 80% or more and 1.0 kg/P or more.
成形物の炭化賦活は、内熱式または外熱式のロータリー
キルン、来車キルン等の加熱炉を使用し、転勤状態、あ
るいは流動状態で行なう。炭化と賦活は、同一加熱炉で
実施してもよく、また、炭化炉と賦活炉を別にして実施
してもよい。炭化過程においては、窒素ガス、燃焼排ガ
ス等のガス雰囲気下で、最終炭化温度600〜1000
℃で実施し、昇温速度は、400℃前後まで100℃/
分以下であれば、成形物の溶着、膨張もない。賦活過程
においては、酸素、水蒸気等の酸化性ガスを含む窒素ガ
ス、燃焼排ガス等のガス雰囲気下、600〜1000℃
に30分〜10時間保持することにより、吸着能の優れ
た、機械的強度の大なる粒状活性炭を得ることができる
。Carbonization activation of the molded product is carried out in a transfer state or a fluidized state using a heating furnace such as an internal heating type or external heating type rotary kiln or a rolling kiln. Carbonization and activation may be carried out in the same heating furnace, or may be carried out in separate carbonization and activation furnaces. In the carbonization process, the final carbonization temperature is 600 to 1000 in a gas atmosphere such as nitrogen gas or combustion exhaust gas.
The heating rate was 100°C/100°C until around 400°C.
If the temperature is less than 1 minute, there will be no welding or expansion of the molded product. In the activation process, the temperature is 600 to 1000°C in a gas atmosphere such as nitrogen gas containing oxidizing gases such as oxygen and water vapor, and combustion exhaust gas.
By holding for 30 minutes to 10 hours, it is possible to obtain granular activated carbon with excellent adsorption ability and high mechanical strength.
実施例1
非粘結炭(VM=30.0%、C5N=1.4Ro=0
.75)と第1表に示す性状の特殊粘結剤を各々アトマ
イザ−で全量100 mesh以下に微粉砕したのち、
第2表に示す配合比で非粘結炭、特殊粘結剤、コールタ
ールを配合し、適当量の水を添加し、ニーダ−にて混練
した。この混練物をディスクペレッターを用いて成形し
、直径5III11、長さ6〜121Wmの円柱状の成
形物を得た。この成形物をロータリーキルンを用いて不
活性雰囲気下、10℃/分で850℃まて昇温炭化した
後、水蒸気を57vo 1%含有する窒素ガスを用いて
850℃で3時間、水蒸気賦活し、第2表に示す性状の
粒状活性炭を得た。Example 1 Non-caking coal (VM=30.0%, C5N=1.4Ro=0
.. 75) and a special binder with the properties shown in Table 1, each was pulverized with an atomizer to a total amount of 100 mesh or less, and then
Non-caking coal, special binder, and coal tar were blended in the blending ratio shown in Table 2, an appropriate amount of water was added, and the mixture was kneaded in a kneader. This kneaded product was molded using a disc pelleter to obtain a cylindrical molded product with a diameter of 5III11 and a length of 6 to 121 Wm. This molded product was carbonized in an inert atmosphere at a rate of 10°C/min to 850°C using a rotary kiln, and then steam activated at 850°C for 3 hours using nitrogen gas containing 57vo 1% of water vapor. Granular activated carbon having the properties shown in Table 2 was obtained.
なお、SO2吸着能は、SO2,2vo1%、H2O,
10vo1%、02.6vo1%、残部N2の合成ガス
を100℃で3時間粒状活性炭に接触させてS02を吸
着させ、測定した。磨耗強度は、JIS−M−8801
に記載のロガ指数測定に使用するドラム試験機に20g
の粒状活性炭を装入し、1000回転させたのち、7
s+eshの篩で篩別し篩上の重量百分率をもって磨耗
強度とした。圧潰強度は、試料より任意に30個の粒状
活性炭を取り出し、水屋式硬度計を用いて1粒づつの圧
潰強度を測定し、30個の平均値をもって圧潰強度とし
た。In addition, SO2 adsorption capacity is SO2, 2vol%, H2O,
Synthesis gas containing 10vol%, 02.6vol%, and the balance N2 was brought into contact with granular activated carbon at 100°C for 3 hours to adsorb S02, and measurements were taken. Abrasion strength is JIS-M-8801
20g to the drum tester used for loga index measurement as described in
After charging granular activated carbon and rotating it 1000 times,
The material was sieved using a s+esh sieve, and the weight percentage on the sieve was defined as the abrasion strength. For the crushing strength, 30 pieces of granular activated carbon were arbitrarily taken out from the sample, and the crushing strength of each grain was measured using a Mizuya hardness tester, and the crushing strength was determined as the average value of the 30 pieces.
なお、比較例として、バインダーにコールタール、軟化
点30℃の軟ピツチおよび軟化点110℃の硬ピツチを
用いた以外、上記と同じ条件で製造した粒状活性炭につ
いても同様の試験を実施した。その結果は第2表に示す
。As a comparative example, the same test was conducted on granular activated carbon produced under the same conditions as above, except that coal tar was used as the binder, and soft pitch with a softening point of 30° C. and hard pitch with a softening point of 110° C. were used. The results are shown in Table 2.
なお、軟化点の測定は、特殊粘結剤についてはフローテ
スター法により、また、軟ピツチ、硬ピツチについては
環球法により測定した。The softening point was measured by the flow tester method for special binders, and by the ring and ball method for soft pitch and hard pitch.
第 2 表
第2表に示すとうり、バインダー中に特殊粘結剤を配合
した本発明の粒状活性炭は、機械的強度が高く、しかも
、SO2吸着能が従来のコールタールピッチ等をバイン
ダーとした活性炭に比較して、約30mg5 O2/
g−AC以上高くなっている。Table 2 As shown in Table 2, the granular activated carbon of the present invention containing a special binder in the binder has high mechanical strength and SO2 adsorption ability compared to conventional coal tar pitch etc. as a binder. Approximately 30mg5 O2/compared to activated carbon
It is higher than g-AC.
また、バインダー中の特殊粘結剤の割合を第2表のごと
く、20〜55wt%と大きく変えても、粒状活性炭は
十分使用に耐えうるものであり、活性炭の製造に当たっ
ては、配合管理が極めて容易である。Furthermore, even if the proportion of the special binder in the binder is greatly changed from 20 to 55 wt%, as shown in Table 2, granular activated carbon can withstand sufficient use, and when manufacturing activated carbon, composition control is extremely important. It's easy.
なお、本実施例においては、非粘結炭とノ(インダーの
比を80:20としたが、この比は用いる非粘結炭の銘
柄によって最適な割合があるべきものであり、本実施例
の割合しこ限定されるものではない。Note that in this example, the ratio of non-caking coal to no(inder) was set to 80:20, but this ratio should be optimal depending on the brand of non-caking coal used. The proportion is not limited.
発明の効果
以上述べたとおりこの発明によれば、)<インダーの一
部として、石油系重質油を熱処理して得た軟化点150
℃以上、H/Co、6〜1.0の特殊粘結剤を配合する
ことによって、吸着能および機械的強度の優れた脱硫用
粒状活性炭を得ることができるから、排煙脱硫のコスト
低減に寄与するところ大なるものがある。Effects of the Invention As described above, according to the present invention, )
By blending a special binder with a temperature of ℃ or higher and H/Co of 6 to 1.0, it is possible to obtain granular activated carbon for desulfurization with excellent adsorption ability and mechanical strength, which helps reduce the cost of flue gas desulfurization. There is a lot to contribute.
Claims (1)
添加剤を添加して混練し、得られた混練物を成形したの
ち炭化・賦活して脱硫用粒状活性炭を製造する方法にお
いて、バインダーの一部として石油系重質油を熱処理し
て得た軟化点150℃以上、H/C0.6〜1.0の特
殊粘結剤を添加することを特徴とする粒状活性炭の製造
方法。In a method of manufacturing granular activated carbon for desulfurization by blending a binder with non-caking coal, adding necessary additives in some cases and kneading, molding the obtained kneaded product, and then carbonizing and activating it, A method for producing granular activated carbon, which comprises adding, as part of the binder, a special binder obtained by heat-treating petroleum-based heavy oil and having a softening point of 150° C. or more and an H/C of 0.6 to 1.0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60020667A JPS61178411A (en) | 1985-02-05 | 1985-02-05 | Production of granular active carbon |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60020667A JPS61178411A (en) | 1985-02-05 | 1985-02-05 | Production of granular active carbon |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61178411A true JPS61178411A (en) | 1986-08-11 |
Family
ID=12033547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60020667A Pending JPS61178411A (en) | 1985-02-05 | 1985-02-05 | Production of granular active carbon |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61178411A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61291940A (en) * | 1985-06-19 | 1986-12-22 | Masaaki Naga | Alloy for metallizing |
WO1999054973A1 (en) * | 1998-04-16 | 1999-10-28 | Siemens Electromechanical Components, Inc. | Quick connect relay module |
KR100462193B1 (en) * | 2001-07-05 | 2004-12-16 | 박상균 | Method of manufacturing an active coal by using a fly ash achieved from the fire power plant |
JP2008100908A (en) * | 2001-07-26 | 2008-05-01 | Kuraray Chem Corp | Formed activated carbon for treating waste gas, and its production method |
CN109835899A (en) * | 2019-04-11 | 2019-06-04 | 上海应用技术大学 | A kind of method that vapor activation prepares lignite base activated coke |
-
1985
- 1985-02-05 JP JP60020667A patent/JPS61178411A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61291940A (en) * | 1985-06-19 | 1986-12-22 | Masaaki Naga | Alloy for metallizing |
JPS6310220B2 (en) * | 1985-06-19 | 1988-03-04 | Masaaki Naga | |
WO1999054973A1 (en) * | 1998-04-16 | 1999-10-28 | Siemens Electromechanical Components, Inc. | Quick connect relay module |
KR100462193B1 (en) * | 2001-07-05 | 2004-12-16 | 박상균 | Method of manufacturing an active coal by using a fly ash achieved from the fire power plant |
JP2008100908A (en) * | 2001-07-26 | 2008-05-01 | Kuraray Chem Corp | Formed activated carbon for treating waste gas, and its production method |
JP4708409B2 (en) * | 2001-07-26 | 2011-06-22 | クラレケミカル株式会社 | Molded activated carbon for waste gas treatment and method for producing the same |
CN109835899A (en) * | 2019-04-11 | 2019-06-04 | 上海应用技术大学 | A kind of method that vapor activation prepares lignite base activated coke |
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